The first electroplating patent was granted in 1842 for the deposition of silver through a cyanide medium. Cyanide then became the electrolyte of choice for many electroplating baths for depositing metals of commercial importance such as gold, silver, copper, cadmium and zinc. The stability of the cyanide compound and tolerance of the chemical to upsets have made cyanide the preferred electrolyte in many electroplating operations.
Cyanide is an extremely toxic and hazardous material, and fumes from electroplating baths have to be destroyed, and waste water containing traces of cyanide have to be extensively treated for disposal. With the nation's new found concern for toxic waste, and also the concern for workers in operations where they could be exposed to cyanide fumes, many attempts have been made to find alternative electrolytes to replace cyanide.
Only a few of the alternative plating bath formulations have been able replace cyanide. Silver, gold and copper electroplates still require cyanide for the first strike on a substrate and are a necessary requirement for all electronic electroplating applications.
With the issuance of the first patents on silver electroplating, there were many attempts made to find other nitrogen compounds which could replace cyanide. Many of early experiments were performed using ammonia as a possible candidate for complexing the silver and gold ions for deposition.
It was found that gold or silver in contact with ammonia compounds formed azides and were violently explosive. Since that time, any ammonia containing compound would not be considered for gold and silver electroplating. Other baths formulated for metals which would not explode when in contact with ammonia, such as copper, zinc and cadmium, were developed using electrolytes other than cyanide. However, cyanide remains the electroplaters electrolye of choice for its stability and efficiency in the plating baths.
Ammonia has been added in minor amounts to many electroplating baths because of its high conductivity and its metal complexing properties. The addition of ammonium hydroxide to the baths are made in such minor amounts that highly exothermic reactions would be avoided. The ammonia fumes, however are less controllable than cyanide fumes and presented strong health hazards in the workplace and in the waste waters. While ammonia is an excellent electrolyte, its uses in electroplating are severely limited in use to minor additions to some plating baths.
The applicants, in attempting to improve upon the throwing power and conductivity of an electroplating bath, found that ammonia could be absorbed into a zinc plating bath without ammonia fumes coming off during the electroplating process. This was not recognized immediately as a major event by the applicants. However, continued experimentation showed that some new, unusual and surprising phenomena were occurring. This continued experimentation led to the attempts to electroplate silver from the baths. A severe explosion occurred, which led to the temporary abandonment of the silver plating process.
Further experimentation resulted in defining that ammonia could be used provided that the ammonia was reacted in a specific way. It was found, surprisingly, that when ammonium hydroxide was contacted by a alkali metal hydroxide in an aqueous medium and then immediately reacted further by the addition of 85 Phosphoric acid (H3PO4), the ammonia was absorbed in the reaction. The solution was then further reacted to reach an end point 7 Ph or lower and become a clear stable, nitrogen containing solution. Classical chemistry teaches that ammonia cannot remain in solution with an alkali metal hydroxide. Therefore, one of the fundamental rules of chemistry apparently becomes inoperative when the elements are reacted in the manner described in this application.
It was then decided to make a further attempt to electroplate silver from the new compounds developed by the described process. Surprisingly, when silver nitrate, or silver oxide was placed in the aqueous solution, there was no azide formation, although ammonia was an essential reactant in the formation of the compounds. The silver was then deposited electrolytically on a steel substrate. This was unexpected. Gold was then electroplated using the same techniques for formulation of the electroplating solution.
The applicants then recognized that a fundamental event had occurred in which ammonia could be absorbed in a solution which contained an alkali metal hydroxide. Further, the ammonia would have to be in altered state, otherwise explosions would have occurred. It was further noted that the silver containing solutions prevented silver from becoming photo sensitive, and the silver could be contained in solution an ionic state indefinitely.
During the further experimentation, it became apparent to the applicants that several unusual new properties appeared to be resident in the solution. These included superior buffering qualities, and that any acid -- including sulfuric and hydrofluoric acids -- and any alkaline could be buffered by the phosphorus based compound. This feature was extremely important when the explosion caused by silver azide formation occurred. McCoy, one of the applicants, was standing viewing the reactor when the explosion occurred and was covered all over his eyes, face and arms with hot boiling alkalis and acids and glass shards.
He was immediately bathed using the phosphoric buffer in his eyes, on his face and arms. The buffer stopped the acid/alkali burns almost instantaneously. An immediate rush visit was made to an eye doctor where glass shards were removed. In two weeks total vision had returned with no residual damage from the acid/alkali burns. Further there was no scarring from the neutralized acid/alkali burns on the face and arms. It was then decided that major therapeutic properties were in the phosphorus compound.
Further reactions were then conducted to determine whether the ammonium hydroxide/alkali metal hydroxide aqueous solution could be absorbed through the chemical reaction with all mineral acids. The acids used were phosphorus species, all halogen species, nitrogen species, sulfur species and carbon species. It was then apparent that ammonia, when reacted in an aqueous solution with other reactants could be changed into a new nitrogen/hydrogen group which provided new chemical compounds through the reaction process. It was further discovered that all the reactants had to be added as rapidly as possible in order to obtain maximum conditions of equilibrium.
Further all of these new compounds had excellent electrolytic properties, could complex metalions, including silver, gold and copper for electroplating, but also exhibited different therapeutic properties when applied to the skin of humans and lower animals. Properties noted were stopping of bleeding from wounds and cuts, disinfections of sores, anti-inflammatory, immediate stopping of pain from cuts and burns, and acceleration of healing without scarring. Further testing showed the compounds to have anti-oxidant properties and could stabilize free radicals. 75% hydrogen peroxide, a powerful oxidant, was stabilized in the phosphorus ad sulfur containing solutions and was meta-stable in the halogen solutions. This indicated the presence of available electrons in the solutions.
Freezing studies were conducted on the compounds. All compounds had changed the freezing point of water. The sodium chloride buffer remained water clear to -23 F., the phosphorus and sulfur and carbon buffers to -10 F. The ice crystals formed by freezing were not the normal tetrahedron ice crystals, and were elongated and slushy. This indicates that a hydrogen bonding mechanism has attached other chemical elements to the water molecule to change the structure of the water. Tests were run with ethylene glycol and methanol and other aldehydes which demonstrates these chemicals were miscible in the new buffers, and could be used as anti-freeze extenders. A further surprising property was that the new compounds picked up and held an electric charge of up 500 milliamperes and 1/2 volt. When bimetallic ions of zinc and silver were added the amperage was raised to 750 milliamperes and the charges maintained. Mixtures of the same chemical ingredients which have not undergone the described reactions have much lower charges in solution. This further indicates the presence of active hydrogen and available electrons.
The compounds can complex any metal ion an ionic state. The compounds can also be formulated of fertilizer components such as phosphorus, nitrogen, potassium, and then a metal ion can be further added by complexing at various parts per million, to act as growth regulators or stimulators, while simultaneously acting as a germicide, if necessary.
The compounds hydrogen ion activity and electron availabilty showed broad spectrum germicidal capabilities. In addition to disinfection on wounds and burns, these properties help augment the acceleration of healing mechanism in the body. Tests on humans and lower animals showed that any topical infection, whether caused by bacterial, viral, fungal or parasitical strains would respond very quickly to treatment with various types of these new compounds.
It was further found that when aluminum was complexed in the phosphorus solution and the Ph raised above 10, that actinic keratosis or "skin cancer" were instantaneously destroyed, and healing accelerated without scarring. The further application of the same aluminum based compounds showed great efficacy on psoriasis. It is theorized that the high electrode potential of the aluminum ion is reponsible for controlling the actinic keratosis.
It is the object of the present invention to provide new nitrogen/hydrogen bearing compounds which allow the combination of elements which could not be combined before is aqueous solutions without salt formation. It is a further object of the present invention to provide a process for the preparation of these new compounds.
As will be readily apparent to those skilled in the art the advantages of these new compounds will be perceived by the following descriptions and the examples.